2-acylamino-1, 3-butadienes



Patented Aug. 3,

UNITED STATES PATENT OFFICE Z-AGYLAMINO-LS-BUTADIENES I Joseph B. Dickey, Rochester, N. Y.. aulsnor to Eastman odak Company, Rochester, N. corporation or New Jersey No Drawing. Application December 22, 1965,

- Serial No. 832,098

'2 Gila-ima- WE. 260-4558) cn==cn-c=cm RNR1 wherein R'represents a member of the group consisting of hydrogen, an alkyl group, an aryl group of the benzene series, and an acyl group;

and R1 represents an acyl group. The term "alkyl" can be methyl, ethyl, propyl, butyl, lauryl and the like groups; and the term aryl" can be a phenyl group, wherein thefree positions can be further substituted by one or more chlorine,

bromine, fluorine or iodine atoms, an alkyl group,

a nitro group, a sulfonamide group. Acyl group can be, for example, acetyl, propionyl, butyryl, I benzoyl. methane sulfonyl, benzene suli'onyl,

furoyl, acryl, amide, alkylamido, arylamido,

wherein R is a carbon chain radical, and similar kind of groups.

The compounds of the invention can be pre: pared by treating 2-aminobutadiene-1,3 or its N-monosubstituted derivatives with acylating agents, and isolating the products thereby obtained. The intermediate 2-amino-L3-butadienes can be prepared by heating the corresponding 2-aminobutine-3 in gas phase to elevated temperatures. The acylating agent can be, !or example, an acid such as acetic acid, butyric acid, an acid halide such as benzoyl chloride. acetyl chloride, an anhydride of a carboxylic. acid, for example, acetic, propionic butyric, phthalic anhydrides, an organic thiocyanate or isocyanate, for example, isocyanic acid, or an organic chlorocarbonate. In some cases, the use of a catalyst, such as sulfuric acid, facilitates the reaction and improved the yield of product.

The 2-acylamino-1,3-butadiene compounds of the invention may be used as starting materials for chemical reactions. They are also useful in the copolymeriration with other vinyl compounds to provide resinous materials which are suitable ll i 2 for making fibers, threads, filaments, films, and

similar kinds or useful products.

' It is, accordingly, an object of my invention to provide new 2-acylamino-1,3-butadiene com- 3 pounds. A further object is to provide a method for preparing the same. Other objects will become apparent hereinafter.

The following exampleswill serve to illustrate my new compounds and the manner of their preparation.

Example I.2-amino-1,3-butadiene The 2-amino-1,3-butadiene and N-monosube stituted derivatives thereof were prepared by the general method described in U. 8. Patent No. 2,301,971, issued November 17, 1942, to Walter Reppe and Otto Hecht, except that 2-aminobutine-3, was passed through a heated porcelain tube at a temperature of 245-25 1; C., and a velocity of about 50 gramsper hour per liter of catalyst. The vapors emerging fromthe tube were condensed and the product purified by fractional distillation at 40-min. pressure.

In place of 2-aminobutlne-3, there can be substituted in the above example z-acetylaminobutine-3 to obtain 2-acetylaminobutadiene-1,3

or 2-N-ethylamlno-butine-3 to obtain N-ethylaminobutadiene-Ld.

Example II.-2-acetylaminobutadiene-1,3

. Ten grams of 2-aminobutadiene-l,3 was suspended in 50 cc. of ice water and 10 grams of acetic anhydrlde slowly added. When all the anhydride had reacted. the product was separated as from the reaction mixture, washed with water and dried.

Example mt-z-b 1izoyzammobumdiene-1,s

Example IV.N-ethul-2-acetylamino-L3- I butadiene Ten grams of 2-N-ethylamino-1,3-butadiene so was suspended in 100 cc. water with 10 grams of acetic anhydride and stirred in the cold until all the anhydride had reacted. The product was removed from the mixture by extraction. with benzene and ether, followed by washing with water.

Example V.--2-N-acetul-N-phen1 lamino-1,3- butadiene Thirteen grams of 2-N-phenylamino-L3-butadiene, 100 cc. of water and 11 grams of acetic anhydride were reacted with stirring in the cold, until all the anhydride had been used up. The compoundwas filtered 011 as a yellowish white solid.

Example VI.-2-diacetylamino-L3-butadiene oms.

2. The compound 2-acetylaminobutadiene-1,3.

3. The compound 2-benzoylaminobutadiene- 1,3. t

4. The compound N-ethyl-2 -acetylamino-L3- butadiene. v

5. The 2-acylamino-L3-butadienes' having the general formula: V

wherein R represents a member selected from the group consisting of hydrogen. an alkyl group of from 1 to 12 carbon atoms and an aryl gro t! of the benzene series, and R1 represents a member selected from the group consisting of the acyl radical of an alkyl carboxyllc acid of from 2 to 5 carbon atoms and the acyl radical of an arylcarboxylic acid of the benzene series.

6. The 2-acylamhm-L3-butadleneshaving the 1 general formula:

cm=cn-c=cm H-NR| wherein R1 represents the acyl radical of an arylcarboxylic acid at the benzene series.

7. The acylamino-1,3 butadienes having the eneral formula: I

CHr=OH-C=CH1 R--NB| wherein R represents an alkyl group of from 1 to 12 carbon atoms and R1 represents the acyl radical of an alkyl carboxylic acid of from 2 to 5 carbon atoms.

JOSEPH, B. DICKEY.

nan-mamas crr'nn The following references are of record in the file of this patent: I

UNITED STATES PATENTS Name Number Date Dykstra etal. Apr. 15, 1941 Reppe et al Nov. 17, 1942 OTHER REFERENCES Muskat et 91.: Jour. Am. Chem. Soc., vol.

, (1933), page 3768.

Carothers et a1 Mar. 9, 1937 Standinger et a]. June 5, 1945 

